Process for treating synthesis product



Sept. 29, 1953 H. v. HEss ET AL PRocEss FOR TREATING SYNTHESIS PRODUCT Filed March 2e, 1949 Patented Sept. 29, 1953 UNITED STATES PATENT OFFICE PROCESS' FOR` TREATING SYNTHESIS PRODUCT Howard V. Hess, Beacon, George-B. Arnold, Glenham, andy Marvin L. Drabkin, New York,.N..Y., assignors. tov The Texas Company, New York, N. Y;,.a corporation. of Delaware ApplicationMarch 26, 1949, Serial-No. 83,732y

(Cl. 26o-45.0).

7 Claims. I.

This invention relates to-a method for treating the' product obtained in.- the catalytic conversion ofsynthesis gas-intosyntheticfuel. More specifically,v the invention discloses a method for separating oxygen-containing` organic compounds from synthesis. product.

In our cop'endin'gapplication, Serial No. 68,463, iiled December 31,1948, entitled rIreatment of Entire Liquid Product in Vapor Phase with Basic Compounds, there is disclosed a process for treating the productobtainedby the catalytic conversionfofcarbon monoxide and hydrogeny into syntheticfuel by contacting it in the vaporphase ata temperatureof. 500 toy 1,000 F. with a basic material such as basic alkali metal compounds, alkaline earth metal compounds and mixtures thereof. The vapor phase basic treatment of synthesisproduct effects hydrolysisv of esters to` alcohols and acids and decarboxylation of acids to hydrocarbons or ketones. Thev recovery of oxygen-containingv organic` compounds is ex'- pedited by conversion of esters'and: acids to: alcohols, hydrocarbons and ketonesv in accordance with the aforedescribed vaporphase basic treatment of= the synthesis product. In still another:

copending application,.namely, Serial No..60,234, ledfiNovember 16, 1948, and entitled Process; for Separating Liquid. Polar Compoundsl from Less Polar Liquid Compounds, of whichtwoY of us are coinventors,.there is disclosed aprocessfor separating polar liquid compounds from less: polar: liquid compounds by contacting a mixture there-- ofin the Vapor phasewith-a particulate-adsorbent which is maintained in. afluent state; Polar.Y compounds areadsorbed err the particulate iluent adsorbent and are recovered therefrom by con-` tacting the adsorbent with a desorbingA gas after the adsorbent hasbeeir separated: from the vaporized mixture. This procedure: for separating: polar compounds from less. polar' compounds is. particularly usefuland applicable to the separation of oxygen-containing organic compounds from gasoline and gas oil fractionsof a4 product obtained by the catalytic conversion: of carbon monoxide and hydrogen intol synthetic fuel.

This invention combinesthe processes of thev above two copending applications into an integrated process containing several cooperative features and thereby expeditesl the. recovery of oxygen-containing organic compounds from synthesis product.

In accordance with this invention, the total synthesis product obtained by the catalytic conversionl of carbon. monoxide and hydrogen into. synthetic fuel is separated into a gas phase and 2 a. liquid phase;l advantageously, this separation into gas and liquid. phases is effected at aA temperaturebetween. 15.0 and 300 F; and at syn.- thesis pressure, i'. e.,. atV av pressure between 1'00 andilopounds per square inch. Thegas phase isv used. as recycle to the, synthesis reaction. The total liquidi phasey isf contacted. withy a= basic compound of anl alkali metal or of an alkaline earth metal or with, mixtures of-i such. basic. compounds whereby oil,- and water-soluble estersi are: hydrolyzed to alcoholszandacidsand oilandwatensoluble acids are decarboxylatedito hydrocarbons or ketones. The base-treated liquid. phase is cooled andv separated: into a water-phase and an oil phase. Thev oil; phase is. theny vaporizedi and contacted with. an; adsorbent: maintained in. a fluentstate whereby alcohols `andfketones present'. in' the oil: phase are'y adsorbed on the fluent ad'- sorbent. Advantageouslyr, a.. portionv of' recycled gas phase employed as a gaseous diluent to aidv inA thefluidization ofv the adsorbent and to help maintain the4 hydrocarbon. phase inthe vapor. state in the adsorption zone.. The adsorbent-is i separated from the vaporized.A oil phase and is introduced. into av desorption zone wherein alcoholsiand; ketoneszare removed therefrom by contacting the= adsorbent materiali with a desorbing. gas= at an elevated temperature while. the ad.- sorbent is maintained inl a uent state. Base-v treated water` phase. which has been converted into. steam'. is= the preferred; gas. for desorption` of oil-soluble alcohols and ketones from the ad sorbent in. thel desorption. zone..

The` catalytic conversion of carbon monoxidek and hydrogen intosyntheticfuel by contact with a fluidized iron catalyst at an elevated tempera--l tureof 500; to 750 F. and at a pressure of 100 to 500; pounds-per square inch results' in the formation of. aproduct mixturecomprising a gas phasey and av liquid phase, the. latter consisting of approximately one part oil phase and two parts water phase; Oxygen-containing organic com. poundsv such as; alcohols, acids, esters, ketones and aldehydes are distributed throughout the twoephaseliquid" product; the molecular weight of. the oxygen-containing compounds determines whether they are primarilyw found iny the Water phase or in the oil phase.. The oxygen-contain.-

ing; organic compounds ordinarily found in theL water phase comprise lower molecular weight Y compounds such as Cito. Cri-alcohols, esters con-l taining up to about 4 carbon atoms, C2 to C6 organic acids and traces of higher molecular weight oxygenated compounds.. The oxygen-containing` organic compounds ordinarily found in the oil phase comprise higher molecular weight compounds such as C4 and higher alcohols, esters containing more than 3 carbon atoms, C3 and higher organic acids and traces of lower molecular weight compounds. The substantial overlapping in the distribution of the oxygencontaining organic compounds is attributable to the fact that compounds of intermediate molecular weight such as C5 alcohols are found in substantial portion in both oil and water phases. The disposal of the water phase in large-scale commercial operations is a serious problem since the oxygen-containing organic compounds comprise as high as 20 per cent of the water phase and their presence would seriously pollute the stream into which the water phase is emptied. Moreover, the oxygen-containing organic compounds present in both oil and water phases are in demand as chemicals of commerce. The present invention provides an integrated process for purifying the water phase so as to alleviate the problem of its disposal and foi` recovering from the synthesis product oxygen-containing organic compounds primarily in the form of alcohols.

Treatment of synthesis product in accordance with the combination process of this invention is characterized by a plurality of advantages. First, the reject water obtained by following the combination process of this invention contains less than 0.2 per cent oxygen-containing organic Y compounds and can be disposed of without causing a serious pollution problem.

A second advantage resides in the fact that the oxygen-containing compounds obtained as a by-product in the formation of synthetic fuel are substantially recovered in the form of alcohols and ketones which greatly simplifies their resolution into individual components. The oxygencontaining compounds are obtained as a mixture comprising approximately 85 per cent alcohols .1

and per cent ketones as a consequence of the combination process of this invention. The resolution of such a mixture is markedly simpler than the resolution of a mixture comprising alcohols, esters, ketones, aldehydes and acids.

A third advantage is realized by the use of a portion of recycle gas phase initially separated from the synthesis product as a diluent in the adsorption zone. The maintenance of the adsorbent in a iiuent state and the preservation of the oil phase in the vapor state are substantially aided by the use of recycle gas phase as a diluent.

The vapor phase treatment of the total liquid product comprising oil and Water phases with a basic material is effected at a temperature between 500 and 1,000 F. and preferably at a temperature between 700 and 950 F. Atmospheric pressure is advantageously employed for contact of the total liquid phase with a basic material in the vapor state but it is also favorable to employ a pressure corresponding to that used for the conversion of synthesis gas into synthetic fuel, that is, pressures between 100 and 500 pounds per square inch.

The basic material employed for the vapor phase contacting of the liquid phase of synthesis product is selected from basic alkali metal hydroxides, alkali metal oxides, alkali metal salts, alkaline earth metal hydroxides, oxides, salts, etc. Sodium carbonate, sodium phosphate, potassium carbonate, potassium borate are examples of basic alkali metal compounds which can be employed in the process of this invention; calcium oxide, calcium carbonate, barium oxide are examples of basic alkaline earth metal compounds used in this invention. Mixtures of alkali metal and alkaline earth metal compounds may also be employed for the Vapor phase basic treatment of the total liquid phase.

The vapor state contacting of the liquid phase with a basic compound is effected at a space Velocity between l and 10 volumes of liquid product per volume of solid basic material per hour. Space velocities between about 2 and 5 are preferred.

Any of the several techniques for catalytic vapor phase contacting can be employed for the base treatment of the liquid synthesis product. For example, the liquid phase of synthesis product in vapor form can be contacted with a fixed bed, uidized fixed bed or a stirred bed of basic particles.

The vapor phase base treatment of the liquid synthesis product results in hydrolysis of oiland water-soluble esters to alcohols and acids and decarboxylation of acids initially present and those formed by ester hydrolysis to either hydrocarbons or ketones. Basic alkali metal compounds eiiect decarboxylation of acids to hydrocarbons whereas basic alkaline earth metal compounds decarboxylate acids to ketones. The base treatment results in a substantial increase in the alcohol content and a substantial decrease in acid and ester contents of both oil and water phases.

The base-treated liquid synthesis product is cooled and separated into a water phase and an oil phase which is diluted with a small amount of gaseous hydrocarbons, such as ethane, methane, ethylene, propylene, propane, butane, butane, etc. which are produced in the base treatment. Water-soluble alcohols and ketones are separated from the water phase. The oil phase is revaporized and contacted with a fluid bed of adsorbent such as silica gel whereby oxygen-containing organic compounds are separated therefrom by adsorption.

The base-treated oil phase is advantageously separated into a gasoline fraction and a gas oil fraction, each of which is independently contacted with an adsorbent for the oxygen-containing organic compounds contained therein. Separation of the oil phase into gasoline and gas oil fractions and independent treatment of each with a fluent adsorbent facilitates the adsorption and recovery of the alcohols and ketones from the oil phase.

The vaporized oil phase either in toto or, as in the preferred modiiication, in separate gasoline and gas oil fractions is contacted with an adsorbent which is maintained in a iluent state in an adsorption zone. Fluent state is used to describe maintenance of an adsorbent in a state of continuous motion as distinguished from a stationary bed of the adsorbent. Fluidized fixed bed, suspension contacting wherein the adsorbent is substantially entrained in the vaporized oil phase, and a moving bed are all modifications of uent operation.

The temperature is maintained between 400 and 700 F. in the adsorption zone. If the gasoline fraction is contacted separately with an adsorbent, the temperature is advantageously maintained in the lower part of the aforedescribed range, that is, between 400 and 500 F. Whereas separate contacting of the gas oil fraction with an adsorbent requires temperatures in the upper part of the range, namely, between 550 and 700 F. If the total oil fraction is contacted with the adsorbent, the temperature is ladvantageously maintained between `600 and 700 F.

The pressure in the adsorption zone is preferably atmospheric but sub-atmospheric and superatmospheric pressures up to approximately 400 lbs. per square inch can be employed. It is, of course, more diilicult to maintain the oil phase in the vapor state at pressures in the upper portion of the aforedescribed range.

The vaporized oil phase is passed through the adsorption zone at a space velocity of approximately 0.5 to 5.0 volumes of liquid oil phase per volume of fluent adsorbent. The space velocity is correlated with the particle size and density of the adsorbent.

The particle size of the adsorbent depends upon the type of iluent operation, adsorbent density and vapor velocity that are employed. Particle size of adsorbent for any particular operation is determined by the vapor velocity; for example, in a fluid bed type operation with vapor velocity of about 1 foot per second, the particle size should be maintained between 50 and 1'5'0 mesh.

Fluent adsorbent containing adsorbed oxygencontaining adsorbed compounds which yare mainly alcohols and ketones is continuously separated from the Vaporized oil phase, removed from the adsorption zone and introduced into the desorption zone. In the desorption zone oxygen-containing organic compounds are desorbed from the f adsorbent by passage of a hot gas through the adsorbent while it is maintained in a iluent state. If the oil phase in toto is contacted with the adsorbent it is advisable to employ a polar desorbing gas such 'as super-heated steam; a portion of the Water phase separated from the base treated liquid synthesis product is advantageously vaporized and employed to effect desorption of oxygen-containing organic compounds from an adsorbent which has been contacted with the total oil phase. Super-heated steam or vaporized base-treated water phase is; also the preferred gas for desorbing oxygen-containing organic compounds which have been separated from the gas oil fraction of oil phase; the oxygen-containing organic compounds separated from the gas oil fraction are practically insoluble in water so that their separation from the condensed aqueous desorbing agent is readily effected. rWhen the gasoline fraction is separately contacted with an adsorbent, a hot gas such as flue Igas or synthesis gas is advantageously used to desorb alcohols and ketones from the absorbent; using such a desorbing agent, the low boiling oxygen- `containing compounds separated from the gasoline fraction are recovered free from water.

The adsorbent is continuously regenerated by contact with the desorbing gas so that it. can be returned to the adsorption zone without further treatment after separation therefrom.

In order that the invention may be more fullyV understood, reference will now be made to the accompanying figure wherein there is. diagrammatically presented a modification of the invention.

Hydrogen and carbon monoxide are introduced from a pipe I into a synthesis reactor 2 wherein conversion of carbon monoxide and hydrogen into liquid hydrocarbons is eiected by contact with an iron catalyst maintained in a fluent state atv a temperature between 500 and 700 F. and at a pressure between 100 and 500 pounds per square inch.

An eiiluent comprising unconverted hydrogen and carbon monoxide, products of reaction comprising water, carbon dioxide, `gaseous and liquid hydrocarbons and oxygen-containing organic compounds, issues from the synthesis reactor 2 through a pipe 3, is introduced into a heat exchanger 4 wherein the product is cooled to a temperature between 150 and 400 F. and preferably to a temperature between 200 and 300 F. without any reduction in pressure. Thereafter, the synthesis eilluent is introduced through a pipe 5 into a separator 'l maintained at a temperature between 150 :and 400 F. and a pressure Ibetween 1"-0 and 500 pounds per square inch. Advantageously, the separator is maintained at a temperature between 200 and 300 F. and at a pressure substantially equivalent to that employed in the synthesis reactor 2. The eilluent is separated into a gas phase and into a liquid phase comprising oil and water phases in the separator l. Separation of the synthesis product into a gas phase and a liquid phase at elevated temperature and pressure relieves the load on the heat exchanger facilities since the liquid product is immediately thereafter raised to a temperature of 500 to 1,000 F. for the vapor phase basic treatment thereof.

The gas phase leaves the separator l through a pipe 8; a major portion thereof is recycled to the synthesis reactor 2 so as to maintain a recycle ratio of recycle gas to fresh feed between 1:1 and 5:1. A pipe 9 serves as a means of removing a minor portion of this recycle gas for use as a. diluent in the vapor phase contacting of the oil phase with adsorbent; draw-off pipe I0 is used to remove unrecycled gas.

The two-phase liquid product is withdrawn from the separator 'I through a pipe I2, introduced into a heat exchanger I3 wherein it is raised to a temperature suicient to vaporize the entire product, that is, a temperature of approximately 500 to 1,000 F. and generally between 700 and 1,000" The liquid product, still under synthesis reaction pressure, is introduced through a pipe I4 into a base-treater I5 containing a basic material of the type heretofore described.

The contacting of the liquid product in the vapor state in the base-treater I5 with a basic compound of an alkali metal or of an alkaline earth metal or of a mixture or" such compounds hydrolyzes oiland water-soluble esters to alcohols and acids and decarboxylates acids initially present together with those formed by ester hydrolysis to either hydrocarbons or ketones. Oiland water-soluble aldehydes present in the synthesis product are polymerized by vapor phase contact with the basic material and are thereafter partially cracked to smaller molecular Weight hydrocarbons and oxygen-containing hydrocarbons. The oiland water-soluble alcohols and ketones are substantially unaffected by the vapor phase basic treatment. The alcohol and ketone content of the liquid product is substantially increased by the vapor phase basic treatment.

The base-treated liquid product with its acid. ester and aldehyde contents substantially reduced but with an increased content of alcohols, hydrocarbons and ketones, is introduced through a pipe I6. into a heat exchanger' I1 wherein it is cooled to a temperature of 150 to 400 F. and. preferably to approximately 250 F. The cooled base-treated product is then introduced through a pipe 20 into a separator 2| wherein it is separated into a gaseous fraction, an oil phase and a water phase.

The base-treated liquid product is advantageously separated into an oil phase and a water phase at an elevated temperature between 150 and 500 pounds per square inch and at an elevated temperature between 150 and 400 F. because normally water-soluble alcohols and ketones are thereby displaced into the oil phase. Moreover, the oil phase immediately after separation is vaporized for contact with a fluent adsorbent, so that heat exchange facilities are relieved by elevated temperature-pressure separation of the base-treated liquid product.

The water phase containing alcohols and ketones is withdrawn from the separator 2l through a pipe 24. Its further treatment will be described hereinafter.

The oil phase diluted with a small amount of gaseous hydrocarbons such as ethane leaves the separator 2| through a pipe 25 and is introduced into a heat exchanger 26 wherein it is raised to a temperature between 500 and 700 F. As indiicated previously the oil phase is advantageously fractionated into gasoline and gas oil fractions which are separately contacted with an adsorbent. However, in the detailed description which fcllows, the total oil phase is contacted with a silica gel in the interests of simplification. Vaporized base-treated water phase is employed to desorb the oxygen-containing organic compounds separated from the total oil phase. As indicated previously, hot ilue gas and synthesis gas are the preferred desorbing gases when the gasoline fraction is treated separately; superheated steam and vaporized base-treated water phase are preferred desorbing gases when the gas oil is separately contacted with an adsorbent.

The heated oil phase diluted with gas phase leaves the heater 26 through a pipe 21 and is combined therein with a portion of the recycle gas phase separated from the total synthesis product. This latter gas phase comprises mainly carbon dioxide and hydrogen together with minor quantities of carbon monoxide and gaseous hydrocarbons.

Vaporized Oil phase flows through the pipe 21 and is introduced into the adsorption zone 30. A hopper 3l is connected with the pipe 2'.' through a pipe 32 and provides a means whereby fresh silica gel adsorbent may be introduced into the adsorption zone 3Q.

In the adsorption zone alcohols and ketones are separated from the vaporized oil phase by adsorption on silica gel. Means are provided for continuously separating the adsorbent from the vaporized oil phase. A settling zone 35 and a cyclone separator 31 are illustrative or" such means.

An effluent from the adsorption zone 30 leaves the separator 5B through a pipe 38. Entrained silica gel is separated in the cyclone separator 31. Thereafter, the effluent, comprising gaseous diluent and vaporized `oil phase substantially free of oxygen-containing organic compounds, is introduced through a pipe 39 into an exchanger 40 wherein it is cooled to atmospheric temperature. The cooled effluent is then passed through pipe 4l into a separator 42 wherein the gaseous diluent is separated from the condensed oil phase.

Gas phase separated from the condensed oil phase in the separator 4Z is recycled through a pipe 43 for further use as a gaseous diluent in the adsorption zone 30. The pipe 43 connects with the pipe 9 through which diluent gas is introduced into the pipe 21 the conduit for introducing vaporized oil phase into adsorption zone 30.

Condensed oil phase leaves the separator 42 through a pipe 45 and is introduced into a fractionating Zone 46 wherein it is separated into gasoline and gas oil fractions. The gasoline fraction is taken off overhead through a pipe 41; the gas oil fraction is withdrawn from the lower portion of the fractionating column 46 through a pipe 48. Both the gasoline and gas oil fractions are substantially free from oxygen-containing organic compounds. The hydroxyl number of both the gasoline and gas oil fractions is less than 1, indicating less than 0.5 weight per cent alcohols. The acid and ester content is negligible.

Silica gel which is removed from vaporized oil phase by means of settling zone 35 and cyclone separator 31 is introduced into a conduit 52 through which it is passed into the desorption zone; standpipes 50 and 5| connect settling zone 35 and cyclone separator 31, respectively, with conduit 52 through which the silica gel containing adsorbed alcohols and ketones is passed into the desorption zone 55. A hot gas carries the silica gel saturated with alcohols and ketones along the conduit 52 into desorption zone 55.

Gases such as methane, nitrogen, carbon dioxide, hydrogen and mixtures thereof may be used to desorb alcohols and ketones from the adsorbent and to simultaneously regenerate the adsorbent. As was indicated previously, vaporized base-treated water phase is a preferred gas for desorbing alcohols and ketones from the adsorbent.

Returning to the treatment of the base-treated Water phase after its separation from the basetreated oil phase in the separator 2| and its discharge therefrom through pipe 24, a major portion thereof is introduced through pipe 24 into a flash tower 51 wherein water-soluble alcohols and ketones are flashed and taken off overhead through a pipe 58 in the form of their aqueous azeotropes. The aqueous azeotropes can be fractionated into individual alcohols and ketones in fractionating columns not shown. A reject water phase is removed from the flash tower 51 through a pipe 59 and may be disposed of by pouring into a river without fear of polluting it. The reject water phase contains less than 0.2 per cent oxygen-containing organic compounds.

A minor portion of the base-treated water phase is diverted from pipe 24 through pipe 60 to a heat exchanger 6I wherein it is vaporized and raised to a temperature of approximately 500 to 800 F. superheated steam containing water-soluble alcohols and ketones leaves the heat exchanger 6I through a pipe 62 and flows into the pipe 52 through which silica gel containing adsorbed oil-soluble alcohols and ketones is transported from the adsorption zone 30 to the desorption zone 55. The superheated steam carries the adsorbent into the desorption zone wherein alcohols and ketones are stripped from the adsorbent by the superheated steam at a temperature of about 600 F. The superheated steam also regenerates the silica gel so that it may be returned to the adsorption zone for separation of further quantities of oil-soluble alcohols and ketones from the oil phase.

A settling zone within the desorption zone 55 and a cyclone separator 66 are employed to separate desorbed and regenerated adsorbent from steam. Standpipes 68 and 69 connect settling zone 65 and cyclone separator 66 respectively With the pipe 21 through which vaporized oil phase is introduced into the adsorption zone 30; regenerated adsorbent is introduced into the pipe 21 by means of standpipes 68 and 69 and is returned through pipe 21 to the adsorption zone 30.

The effluent from the desorption zone 55 comprises steam, oil-soluble alcohols and ketones and a small portion of Water-soluble alcohols and ketones. The effluent is introduced through a pipe 10 into the cyclone separator 55 wherein entrained silica gel is separated, and is thereafter introduced into a heat exchanger 1I through a pipe 12. The eilluent is cooled to atmospheric temperature in the exchanger 1I and is introduced through a pipe 13 into a separator 14 in the form of a condensate. The pipe 82 serves to remove uncondensed material from separator 14. Oil-soluble alcohols and ketones which are substantially insoluble in water are withdrawn from the separator 14 through a pipe 15. These oil-soluble alcohols and ketones can be fractionated into individual components in fractionating apparatus not shown.

Water, containing Water-soluble alcohols and ,ketones is withdrawn from the separator 14 through pipe 'it and after having been heated in an exchanger 11 is introduced through a pipe 18 into a flash tower 19. In the ash tower 19 water-soluble alcohols and ketones are flashed from the water in the form of their alcoholand ketone-water azeotropes which are taken off overhead through a pipe 8|). Reject water is withdrawn from the flash tower 19 through a pipe 8|. This reject water phase also contains less than 0.2 per cent oxygen-containing organic compounds and can be disposed of without causing a pollution problem.

The foregoing detailed description presents a modification of the combination process of the present invention. It will be recognized that many modifications may be made in the above detailed description. Adsorbents other than silica-gel, separation temperatures other than those recommended are alternatives which may be employed. Moreover, it is recommended that the oil phase be separated into gasoline and gas oil fractions which are separately contacted in the vapor state with a fluent adsorbent.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the ap- I pended claims.

We claim:

l. A process for treating a product containing water, hydrocarbons and oxygen-containing organic compounds comprising alcohols, esters, acids, aldehydes and ketones and which is obtained by the catalytic conversion of carbon monoxide and hydrogen into synthetic fuel which comprises separating the synthesis product obtained by catalytic conversion oi synthesis gas into a gas phase and a liquid phase comprising oil and water phases, contacting said entire liquid phase in the vapor state at a temperature 0f 500 to 1,000 F. with a solid -basic material selected from the group consisting of alkali metal compounds, alkaline earth compounds and mixtures thereof whereby esters are hydrolyzed to alcohols and acids and acids are decarboxylated to hydrocarbons and ketones, cooling said base-treated liquid phase, separating said base-treated liquid phase into an oil fraction and a water fraction, vaporizing said oil fraction containing oxygenates mainly in the form of alcohols and ketones, contacting said oil fraction with a particulate adsorbent at a temperature of 400 to 700 F.

whereby said oxygen-containing organic compounds, mainly alcohols kand ketones, are adsorbed on said adsorbent, separating said adsorbent containing oxygen-containing organic compounds adsorbed thereon from said vaporized oil fraction and recovering oxygen-containing or-` ganic compounds comprising mainly alcohols and ketones from said separated adsorbent.

2. A process according to claim l in which the particulate adsorbent is silica gel.

3. A process for treating a product containing water, hydrocarbons and oxygen-containing organic compounds comprising alcohols, esters. acids, aldehy-des and ketones and which is ob'- tained by the catalytic conversion of carbon monoxide and hydrogen into synthetic fuel, which comp-rises separating the synthesis product 0btained by catalytic conversion of synthesis gas into a gas phase and a liquid phase comprising oil and water phases, contacting said entire liquid phase in the vapor state at a temperature of 500 to 1,000 F. with a solid basic material selected from the group consisting of alkali metal compounds, alkaline earth compounds and mixtures thereof whereby esters are hydrolyzed to alcohols and acids and acids are decarboxylated to hydrocarbons and ketones, cooling said base-treated liquid phase, separating said base-treated liquid phase into an oil fraction and a Water fraction, vaporizing said oil fraction containing oxygenates mainly in the form of alcohols and ketones, contacting said oil fraction with a particulate fluent adsorbent at a temperature of 400 to 700 F. whereby oxygen-containing organic compounds,

^" mainly alcohols and ketones, are adsorbed on said adsorbent separating said adsorbent containing oxygen-containing organic compounds adsorbed thereon from said vaporized oil fraction, introducing said adsorbent into a desorption zone, contacting said adsorbent With a desorbing gas at elevated temperature whereby oxygen-containing organic compounds are desorbed from said adsorbent and recovering said desorbed oxygencontaining organic compounds comprising mainly alcohols and ketones.

4. A process according to claim '3 in which a portion of vaporized base-treated Water phase is used as the desorbing gas at a temperature between 500 and 800 F.

5. A process for treating a product containing Water, hydrocarbons and Oxygen-containing organic compounds comprising alcohols, esters, acids, aldehydes and ketones and which is obtained by the catalytic conversion of carbon monoxide and hydrogen into synthetic fuelI which comprises separating the synthesis product obtained by catalytic conversion of synthesis gas into a gas phase and a liquid phase comprising o1l and water phases, contacting said entire liquid phase in the vapor state at a temperature of 500 to l,000 F. With a solid basic material selected from the group consisting of alkali metal compounds, alkaline earth compounds and mixtures thereof whereby esters are hydrolyzed to alcohols and acids and acids are decarboxylated to hydrocarbons and ketones, cooling said base-treated liquid phase, separating said base-treated liquid phase into an oil fraction and a Water fraction. vaporizing said oil fraction containing oxygenates mainly in the form of alcohols and ketones, combining a portion of said gas phase separated from synthesis product with said vaporized oil fraction, contacting said oil fraction and gas phase with a particulate fluent adsorbent at a temperature of 400 to 700 F. whereby oxygen-containing organic compounds, mainly alcohols and ketones, are adsorbed on said adsorbent, separating said adsorbent from said vaporized oil phase, introducing said adsorbent into a desorption zone, contacting said adsorbent with a vaporized portion of said base-treated water fraction at an elevated temperature of 500 to 800 F. whereby oxygen-containing organic compounds are desorbed from said adsorbent and recovering said desorbed oxygen-containing organic compounds comprising mainly alcohols and ketones.

6. A process for treating a product containing water, hydrocarbons and oxygen-containing organic compounds comprising alcohols, esters, acids, aldehydes and ketones and which is obtained by the catalytic conversion of carbon monoxide and hydrogen into synthetic fuel, which comprises separating the synthesis product obtained by catalytic conversion of synthesis gas into a gas phase and a liquid phase comprising oil and Water phases, contacting said entire liquid phase in the vapor state at a temperature of 500 to 1,000 F. with a solid basic material selected from the group consisting of alkali metal compounds, alkaline earth compounds and mixtures thereof whereby esters are hydrolyzed to alcohols and acids and acids are decarboxylated to hydrocarbons and ketones, cooling said base-treated liquid phase, separating base-treated liquid phase into an oil fraction and a water fraction, dividing said oil fraction into a gasoline fraction and a gas oil fraction, vaporizing said gasoline and gas oil fractions containing oxygenates mainly in the form of alcohols and ketones, contacting said gasoline fraction and said gas oil fraction indi- CII vidually with particulate fluent adsorbents, at a. temperature of 400 to 700 F. whereby oxygencontaining organic compounds, mainly alcohols and ketones, are adsorbed on said adsorbents, separating said adsorbents from said gasoline and gas oil fractions, separately treating the adsorbents from the gasoline fraction and the gas oil fractions in desorption zones with a vaporized portion of said base-treated water fraction at an elevated temperatures oi' 500 to 800 F. whereby oxygen-containing organic compounds are desorbed from said adsorbents and recovering said desorbed oxygen-containing organic compounds comprising mainly alcohols and ketones.

7. A process according to claim 6 in which the adsorbent is silica gel.

HOWARD V. HESS.

GEORGE B. ARNOLD.

MARVIN L. DRABKIN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,577,534 Miller Mar. 23,1926 1,684,640 Schmidt et al Sept, 18, 1928 2,410,642 Farkas et al. Nov. 5, 1946 2,425,535 Hibshman May 12, 1947 2,449,402 Lipkin et al. Sept. 14, 1948 2,457,257 Michael et al. Dec. 28, 1948 2,523,149 Scheeline Sept. 19, 1950 FOREIGN PATENTS Number Country Date 350,502 Great Britain June l5, 1931 

1. A PROCESS FOR TREATING A PRODUCT CONTAINING WATER, HYDROCARBONS AND OXYGEN-CONTAINING ORGANIC COMPOUNDS COMPRISING ALCOHOLS, ESTERS, ACIDS, ALDEHDES AND KETONES AND WHICH IS OBTAINED BY THE CATALYTIC CONVERSION OF CARBON MONOXIDE AND HYDROGEN INTO SYNTHETIC FUEL WHICH COMPRISES SEPARATING THE SYNTHESIS PRODUCT OBTAINED BY CATALYTIC CONVERSIONM OF SYNTHESIS GAS INTO A GAS PHASE AND A LIQUID PHASE COMPRISING OIL AND WATER PHASES, CONTACTING SAID ENTIRE LIQUID PHASE IN THE VAPOR STATE AT A TEMPERATURE OF 500 TO 1,000* F. WITH A SOLID BASIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL COMPOUNDS, ALKALINE EARTH COMPOUNDS AND MIXTURES THEREOF WHEREBY ESTERS ARE HYDROLYZED TO ALCOHOLS AND ACIDS AND ACIDS ARE DECARBOXYLATED TO HYDROCARBONS AND KETONES, COOLING SAID BASE-TREATED LIQUID PHASE, SEPARATING SAID BASE-TREATED LIQUID PHASE INTO AN OIL FRACTION AND A WATER FRACTION, VAPORIZING SAID OIL FRACTION CONTAINING OXYGENATES MAINLY IN THE FORM OF ALCOHOLS AND KETONES, CONTACTING SAID OIL FRACTION WITH A PARTICULATE ADSORBENT AT A TEMPERATURE OF 400 TO 700* F. WHEREBY SAID OXYGEN-CONTAINING ORGANIC COMPOUNDS, MAINLY ALCOHOLS AND KETONES, ARE ADSORBED ON SAID ADSORBENT, SEPARATING SAID ADSORBENT CONTAINING OXYGEN-CONTAINING ORGANIC COMPOUNDS ABSORBED THEREON FROM SAID VAPORIZED OIL FRACTION AND RECOVERING OXYGEN-CONTAINING ORGANIC COMPOUNDS COMPRISING MAINLY ALCOHOLS AND KETONS FROM SAID SEPARATED ADSORBENT. 